Textile material coated with a waterproofing agent

ABSTRACT

COMPOUNDS OF THE FORMULA   B-CO-NH-R-NH-CO-A   (WHERE R IS TOLYLENE OR HEXAMETHYLENE: A AND B ARE NHR1, NHR2, N(R1)2, N(R2)2, OR1, R1 OR R2; AND R1 AND R2 ARE ALIPHATIC HYDROCARBON RADICALS OF 12-22 CARBON ATOMS) ARE CROSSLINKED ON TEXTILE FABRICS WITH ISOCYANATES TO PROVIDE EFFECTIVE AND LONG LASTING WATERPROOFING OF THE FABRIC.

Patented Jan. 29, 1974 3,788,884 TEXTILE MATERIAL COATED WITH AWATERPROOFING AGENT Andr Bernard, Pierre Gagne, and Georges Gras,V1lleurbanne, and Jean Neel, Lyon, France, assignors to Societe Civiledite Soltex, Paris, France No Drawing. Original application Dec. 16,1969, Ser. No. 885,620. Divided and this application Feb. 16, 1971, Ser.No. 115,805 Claims priority, application France, Dec. 19, 1968, 50,775;Nov. 6, 1969, 6938618 Int. Cl. B44d 1/02 US. Cl. 117-121 2 ClaimsABSTRACT OF THE DISCLOSURE Compounds of the formula B-CONHRNHCO-A [whereR is tolylene or hexamethylene; A and B are n z, 1)2, 2)2 1, 2 1 or 2;and R and R are aliphatic hydrocarbon radicals of 1222 carbon atoms] arecrosslinked on textile fabrics with isocyanates to provide eifective andlong lasting waterproofing of the fabric.

The present application is a divisional application of US. Ser. No.885,620, filed Dec. 16, 1969.

The present invention relates to new agents for making textileswater-repellent. It also relates to a process of applying these agentsto textiles.

Many products are known for waterproofing textiles, e.g. paraffinicwaxes; aluminium soaps; complex con1- pounds of chromium;N-methylolamides of fatty acids; pyridinium salts; condensation productsof melamineformol, ureas and formol, and phenol-formol; perfiuorinatedorganic compounds; silicones; etc. But those products generally give atemporary water-repellency as they are removed little by little duringrepeated washings and degreasings of fabrics on which they are applied;this disadvantage is even more apparent when the agents used have astructure not allowing them to react with fabric cellulose and/or whenthey are used for treating textile materials on which they cannot bebound chemically. Moreover when those compounds are deposited on fabricsin the form of aqueous dispersions, it is necessary to add emulsifyingagents to improve wetting; however, those hydrophilic products decreasethe effect obtained by waterproofing agents.

It is a prime object of the present invention to provide new productsand a process for their application, which obviates the preciteddisadvantages, and this has now been accomplished. One aspect of theinvention relates to organic compounds intended for waterproofingtextiles. Another aspect relates to a process of applying thosecompounds, providing an excellent water-repellency to all the types oftextile materials, such water-repellency having especially the advantageof permanency, that is the ability to resist to repeated washings anddegreasings.

The new waterproofing agents according to the invention are organiccompounds having the general formula:

in which R is a tolylene or hexamethylene radical, A and B, identical ordifferent, may be groups NHR, or NHR N(R or N(R OR, or 0R R or R inwhich R and R identical or different, are aliphatic hydrocarbon radicalsof the formula C H L n being an integer comprised between 12 and 22.

Those compounds exist under normal conditions in the form of whitecrystalline solids, quite soluble in hot, usual organic solvents such asaromatic hydrocarbons, as benzene, toluene, or chlorinated aromatichydrocarbons such as mono-, di-, trichlorobenzenes. In cold solventstheir solubility is variable according to the particular compounds;however, even when cold their solubility is generally sufficient for thecontemplated application, in solvents such as l,2-dichloro, or1,3,5-trichloro-benzene, or nitrobenzene.

Those compounds may be obtained by means of any classical techniques inthe field of the contemplated products. As an example, they may beformed from tolyleneor hexamethylene-diisocyanate. Tolylene diisocyanatemay be constituted by a mixture of isomers and especially be thecommercial product containing 20% isomer 2,6 and 80% isomer 2,4 knownunder the name of Desmodur T80 (registered trademark). About symmetricderivatives, that is derivatives of which the radicals A and B areidentical, bis-ureas may be prepared by reaction of the convenientisocyanate and amine, in an organic solvent which is inert underreaction conditions, specially a chlorobenzene or acetone. Biscarbamatesare obtained by heating of convenient isocyanate and alcohol in an inertsolvent in the presence of a tertiary amine as a catalyst. Or bis-amidesmay be prepared by reacting hexamethylene or tolylene-diisocyanate withan aliphatic acid, in the presence of a catalyst which may be a tertiaryamine.

The asymmetric derivatives may have either different hydrocarbonradicals R and R or different functional groupsureacarbamateamide, orthose two differences at the same time. In the first case the compoundsare obtained by means of the precited methods in reacting simultaneouslyon isocyanate the two types of necessary reagents; in the other cases atwo-stage process is necessary.

Examples of the present compounds are hexamethylenebis (3 octadecylurea)hexamethylene-bis-octadecanamide; hexamethylene-bis (O-tetradecylcarbamate); the 2,4 and 2,6 isomers, alone or in admixture, oftolylene-bis(3- dodecylurea), of tolylene-bis(3-tetradecylurea), oftolylene-bis(3 hexadecylurca), of tolylene-bis( 3 octadecylurea), oftolylene-bis(3-dioctadecylurea), tolylene-bis (O- tetradecyl carbamate),tolylene-bis (O-octadecyl carbamate), of tolylene-bis (O-eicosylcarbamate), of tolylenebis-hexadecanamide, oftolylene-bis-octadecanamide, of tolylene(3-dodecylurea-3-octadecylurea), of N[(3-octadecylureido) tolylene]octadecanamide, and of octadecyl N[(3-octadecylureido) tolylene]carbamate.

The process of applying such waterproofing agents to textiles, which isalso an object of the present invention, consists'essentially ofimpregnating textiles with organic solutions of such agents, then ofcross-linking the agents by means of polyisocyanates. Practically theprocess is generally carried out by providing organic solutions of thewaterproofing agent, to which is added the polyisocyanate used forfurther cross-linking, and possibly a catalyst of known type whichaccelerates this reaction, then in applying this solution on the fabricby any classical method such as spraying or padding, and then, aftersolvent removing, in submitting the fabric to a thermal treatment inorder to obtain cross-linking.

The concentration of the waterproofing agent in the organic solution mayvary within large limits. It is, however, advantageous to use between 20and gm. per liter of solution. The solvents which may be used are theones which have been quoted hereinabove as suitable for dissolving thecompounds of Formula I in the hot or cold. At the hereinabove givenconcentrations the obtained solutions are slightly viscous and have atranslucid appearance.

As isocyanates for cross-linking the waterproofing agents, all the typesof known diand polyisocyanates may be used, and for examplehexamethylene-diisocyanate or its reaction product with water having thecommercial name of Desmodur N (registered trademark);tolylene-diisocyanate and especially the mixture of precited isomers,known under the name of Desmodur T80; diphenyl-methane diisocyanate; themixture of diphenylmethane diisocyanate and of its higher homologshaving the commercial name of Desmodur VL (registered trademark); apolyisocyanate having an isocyanurate structure, such as Desmodur IL(registered trademark); a triisocyanate resulting from condensingtrimethylol propane and tolylene diisocyanate, such as Desmodur L(registered trademark), etc. The quantity of isocyanate to be used mustbe at least equal to that theoretically necessary to cross-link thewaterproofing agent. However, it is preferred to use an excess ofisocyanate, for example, 50 to 150% excess, i.e. ISO-250% based on 100%agent.

As stated above, it is possible to add to the solution catalysts ofknown type, which accelerate the reaction between waterproofing agentand polyisocyanate. The convenient accelerating agents are, for example,tertiary amines such as methyl diethyl amine, triethyl amine, N- methylmorpholine, organo-metallic compounds, such as tetramethyl tin, dibutyltin dilaurate, metal salts of organic acids such as zinc octanoate,cobalt naphthenate, etc.

It is interesting to note that the mixtures prepared in this way,containing the derivative of Formula I in solution, polyisocyanate andoptionally, reaction accelerating agent, are stable in the cold and maybe kept as such for several days. They are applied on fabrics at roomtemperature or at a higher temperature, for example at 50 80 C.

As stated above, the textile material is impregnated according toclassical technique such as spraying or padding, followed by squeezing.The quantity of impregnating solution is adjusted, taking into accountits concentration, in order to obtain the desired proportion of dryextract (calculated on the basis of waterproofing agent +polyisocyanate)on fabric. This proportion is favorably comprised between 0.5 andpreferably 1 to 3% with regard to the weight of the treated textile.

After solvent removing cross-linking is induced in situ by submittingthe fabric to a thermal treatment. The applied temperatures are in arange which is not harmful for treated textiles. Indeed it is operatedat temperatures, which, with regard to the used polyisocyanate, vary ina general way between 100 and 150 C. The reaction is quick enough; thus,after a treatment time of 3 to 4 minutes, it is possible to have asufficient cross-linking. Generally, a complete reaction is obtained insubmitting fabric to precited temperatures during a time which does notexceed min. and which is, the most usually, from 5 to 7 minutes.

The new waterproofing agents and the application process according tothe invention, may be used for all the types of textiles, constitutedeither by natural fibers such as cotton, linen, wool or blends, orartificial fibers such as viscose, rayon, cellulose acetates, orsynthetic fibers such as polyacrylic fibers, polyesters, polyamides, orstill by their mixtures as for example associations polyestercotton,polyester-viscose, etc. They are especially interesting for synthetictextiles such as polyamides, which, it is known, are the most difiicultto hydrofuge. The obtained waterproofing is at the beginning generallysuperior than the one brought about by known products and it resistsconveniently to washings and/ or degreasings much better than the knownmaterials.

The examples hereinafter, given in a non-limitative way, furtherillustrate the object of the invention. Examples 1 to 5 describe thepreparation of waterproofing agents. The following examples relate totests of waterproofing various textiles.

EXAMPLE 1 For this test a device has been used which was contituted by areactor provided with a stirrer, a thermocouple, a system forintroducing isocyanate and surmounted by a cooler.

300 kg. of monochlorobenzene and 50 kg. of octadecylamine were fed tothe reactor. The mixture was brought to C.; then there was introducedduring 1 hour under strong stirring, 16 kg. of Desmodur T80(tolylene-diisocyanate with 80% of isomer 2,4 and 20% of isomer 2,6)maintaining temperature between and C. After cooling, the reactionmixture was filtered, then the isolated white solid was washed withacetone. After drying there was recovered 62.7 kg. of a product meltingat 175 C.

The product has been identified as being a mixture of the 2,4 and 2,6isomers of tolylene-bis (3-octadecylurea).

Results of elemental analysis.Calculated (percent): C, 75.78; H, 11.87;N, 7.85. Found (percent): C, 75.70; H, 11.86; N, 7.77.

In operating under the same conditions as hereinabove, but in replacingDesmodur T by hexamethylene-diisocyanate, there was obtainedhexamethylene-bis (3-octadecyl-urea) melting at 175-l76 C.

EXAMPLE 2 In a device identical to the one of Example 1, there wasloaded kg. of acetone and 80 kg. of dioctadecylamine, at roomtemperature. Then there was introduced in 45 min. under strong stirring13.4 kg. of Desmodur T80 in solution in 50 kg. of acetone, maintainingthe temperature near 30 C. After the end of addition, the reactionmixture was heated under reflux for 1 hour. After cooling, the formedwhite crystalline solid was isolated by filtration; after air drying, itweighed 80 kg.

This product, the melting point of which is 53-55 C., has beenidentified as being a mixture of the 2,4 and 2,6 isomers of tolylene-bis(3-dioctadecylurea)-(nitrogen content: calculated 4.60; found 4.65).

EXAMPLE 3 In a device of the same type as in Example 1, there wasintroduced 1 kg. of trichlorethylene, 320 g. of 1- octadecanol and 1 g.of triethylamine, to which 110 g. of Desmodur T80 was added slowly.After cooling at 20 C. the reaction mixture was filtered and theisolated white solid was washed with acetone; this solid had a weight of330 g. and has been identified as being a mixture of the 2,4 and 2,6isomers of tolylene-bis (O-octadecyl carbamate). Its melting point is90-92 C. (nitrogen content: calculated 3.92; found 4.03).

EXAMPLE 4 To a mixture of 1 kg. of octadecanoic acid and 5 gm. oftriethylamine, heated to 180 C., was added 306 g. of Desmodur T80, understirring. After the addition the mixture was maintained at l70l80 C.during 2 hr. 30 min. Then it was cooled to 100 C., cast, and thereafterground. There was recovered 1.140 kg. of a white solid identified asbeing a mixture of 2,4 and 2,6 tolylene (bisoctadecanamide); aftercrystallization from dimethylformamide, this product melts at 133-135 C.(nitrogen content: calculated 4.27; found 4.20)

EXAMPLE 5 Octadecyl N-[(3-octadecyl-ureido) tolylene] carbamate wasprepared in a 2 stage process by reacting first tolylenediisocyanatewith l-octadecanol (molar ratio 1/ 1) in acetone, then introducing thenecessary quantity of octadecylamine (1 mole per isocyanate mole), andat last filtering the reaction mixture for isolating the formed whiteprecipitate. Then the product was washed with acetone and dried.

EXAMPLE 6 A solution of 50 g./l. of tolylene-bis (3-octadecylurea) fromExample 1 was prepared in o-dichlorobenzene, by introducing understirring the bis-urea into the solvent previously heated to 80 C. Thenafter cooling to 20 C.,

6 two formulations were made from this solution by addper liter ofo-dichlorobenzene was padded at C., then ing: dried at C. Then thefabric was submitted to a tem- I h fir t case; perature of 130 C. during5 mintues. The deposit of dry Desmodur T 25 ri l on the fabric was 3.0%.Zn octanoate 02 5 In a comparative way, two samples of fabric dentical Ithe second case; to the previous one Were treated in the same conditionsas Desmodur VL 1 30 but i g i ilme, Instead of the products of the Znoctanoate n I n ()2 mvm'ltlon, known proofing agents applled accordingto their own techniques, that is: Mixture of primarily diphenyl methanediisocyanate and 10 of its higher homologs (considered as purediphenylmethane Formula gr. /1 of ffi i Wax added i metal diisocy-anatein the calculation for the test).

11c salts, and applied as an aqueous emulslon Then 2 paces ofPOWester/cotton fabnc w Padfied Formula B: gr./l. of stearylatedmelamine/formol at room temperature, using the two formulations (1 pieceresin applied as an aqueous emulsion brought to PH per formulation) inorder to have a deposit of about 45 by addition of acetic acid 2.0% ofdry material on the fabric. They were dried at 15 60 C. and submitted toa thermal treatment of 5 min- Then those different samples weresubmitted to washutes at C. Then half of each fabric respectively wasings, degreasings and to Schmerber test, as described in the washed ordegreased several times, and applied to them previous examples.Moreover, another test, also classical after the first and fifthoperations was the Schmerber in textile industry, was made on thosefabrics, with the test, well known in textile industry (standard Afnor20 help of the apparatus called Spray Tester (see Afnor 607-057). Thistest consists of measuring the maximal Standard G07-056 and ASTMStandard D583-63). This pressure of mm. Water which may be borne, bfabri test measures the Wettability of fabrics and the results arebefore passage therethrough. (The test was also applied expressedaccording to the following scale:

ft trn f h a er trea be ore was mg or degreasmg 1Complete wetting of thehole watered surface Washings were made by treatment at 60 C. during 2530 minutes with an aqueous solution of 5 g./1. of soap and 2 g./l. ofsodium carbonate (according to standard I803). Degreasings were achievedby means of perchlor- 2Wetting of more than the half of watered surface3Wetting of the watered surface, only on small separated zones ethyleneat 20 C., during 30 minutes. 4No wetting, only small droplets adhere tothe watered The obtained results are given in the Table 1 herein- 30Surface after: 5No wetting and no droplet on the watered surface.

TABLE 1.RESULTS 0F SCHMERBER TEST (mm. water) After After After AfterAfter 5th treatfirst first 5th dement washing degreasing washinggreasing First formulation 180 180 190 185 Second formulation 180 195140 EXAMPLE 7 The obtained values are given in Table 3 hereinafter.

The numbers correspond to the average of 4 measures achieved in 4different points of the samples.

As it may be seen, the waterproofing degree given to 5 fabrics by thetechniques according to the invention, and

valued according to Schmerber test is still higher, after 5 Cottonfabrics were treated in the same conditions and with the sameformulations as in Example 6. Then they were submitted to the same testafter washings and degreasings, as explained previously. The results arereproduced in the Table 2 hereinafter.

TABLE 2.RESULTS OF SOHMERBER TEST (mm. water) After After After AfterAfter 5th treatfirst first 5th dement washing degreasing washinggreasing First formulation 330 200 200 200 200 Second formulation 210240 210 220 EXAMPLE 8 washings or degreasings, than the one initiallybrought by A sample of polyamide 6-6 taffeta in a solution conthetechniques of prior art. Wettability numbers are also taining 50 g. oftolylene-bis (3-octadecylurea) of Example quite satisfactory while theresults become quickly bad 1, 39 gr. of Desmodur VL and 0.2 gr. of zincoctanoate, with Formulae A and B.

TABLE 3 Fabric treated According to the invention With Formula A WithFormula B Spray- Sprayp y- Schmerber tester Schmerber tester Schmerbertester Measurement results after- Treatment 225 5 76 5 82 6 180 4 75 375 1 160 4 80 2 57 1 152 8 67 2 60 1 106 3 07 2 31 1 104 3 65 2 35 1 1374 50 2 67 1 132 4 38 1 36 1 137 4 50 1 50 1 120 4 60 1 24 1 106 3 34 122 1 7 8 EXAMPLE 9 said compound being cross-linked with apolyisocyauate There were prepared solutions at gr./l. in orthodiin thePresence of an acceleratorchlorobenzene, of every one of the compoundsof Exam- 2. A cross-linked waterproofing coating on a textile ples 2through 5, by dissolution of said compounds in the comprising; solvent,under stirring, at room temperature. Then from these solutions twoseries of formulations were made, by a compound havmg the formulaadding:

For the first series: G./l.

Desmodur T 25 Cobalt naphthenate 0.2 10 l For the second series:

Desmodur VL 39 Cobalt naphthenate 0.2

These 8 compositions were used to pad samples of poly- 15 amide toobtain a deposit of 2 to 3% of dry mate wherein R is a tolylene orhexamethylene radical,

rial on the fabric. Those fabrics were dried at C. A and B are selectedfrom the group consisting of and a thermal treatment of 5 minutes wasapplied to NHR1, z, 1)z z)z 1 2 1 and 2 them at l30 C. in which R and Rare selected from the group con- The dlfierent Samples were Submltted towashmgs 20 sisting of aliphatic hydrocarbon radicals of formulagreasings, Schmerber test and spray-tester as described in the previousexamples C H t n being an integer between 12 and 22, in-

The obtained results are shown in the Table 4 hereinclusive;

after. said compound being condensed with a polyisocyanate.

TABLE 4 Fabric treated with the product of Example Formulation (series)1st 2d 1st 2d 1st 211 1st 2d Tests Sch. Sp. Sch. Sp. Sch. Sp. Sch. Sp.Sch. Sp. Sch. Sp. Sch. Sp. Sch. Sp.

Results after- Treatment 12s 4 120 6 140 5 130 5 140 11 125 5 5 130 55th washlng 4 4 10 a 3 70 3 70 4 80 a 95 a 5th degreasing 90 a 105 3 803 80 4 90 4 80 a 75 3 a No'rE.-Schmerber Test (Sch.)results given in mm.water; Spray-tester" (Sp.).

The values reproduced above show that the water- References Citedproofing degree of polyamide fabrics is maintained at a UNITED STATESPATENTS satisfactory level, even after 5 washings or degreasings. 40

Whatis claimedis, 2,314,968 3/1943 Berstian et al. 117 139.5 A

1. Adried coatin onatext'l com risin 2,343,920 3/1944 Maxwell 117-4395CQ acompound havifigthe fi p g 2,446,864 8/1948 Abrams 117 143 A2,555,745 6/1951 Hopkins et al. 117l38.8 U A 3,119,865 1/1964 Weakley eta1. 260-553 A C N C A 45 3,384,606 5/1968 Dieterich et a1. 117-161 KP3,392,148 7/1968 Zech et a1. l17--161 KP FOREIGN PATENTS 118,839 8/1944Australia 117DIG. 7

wherein R is a tolylene or hexamehtylcne radical, A 50 and B areselected from the group consisting of WILLIAM MARTIN Pnmary Exammer NHRNHR N(R N(R 0R 0R R and T. G. DAVIS, Assistant Examiner R, in which Rand R are selected from the group consisting of aliphatic hydrocarbonradicals of for- ."U.S. Cl. X.R.

mula CnHZnw being an integer betwm 12 and 55 117-138.8 F, 138.8 N, 138.8UA, 141, 143 R, 144 22, inclusive;

3,788,884 January 29, 1974 Patent No. Dated Invehtor( et a].

It is certified that error appears in the above-identified patent andthat saidLetters Patent are hereby corrected as shown below:

Column 5, line 20, "Afnor" should read --AFNO Column 5, Table 2, "330"should read --220-- Column 6, line 20, "Afnor" should read --AFNOR--Column 6, line 24, "hole" should read whole-- Signed and sealed this'lthday of July 1971 *(SEAL) I Atte stz I M'ccoY M, GIBSON, JR. c. MARSHALLDANN I Attesting fOffi cer j Commissioner of Patents FORM Po-ws'o(10-69) I USCOMM-DClO376-P69 Q U.S. GOVERNMENT PRHITING OFFICE "l9O-366-3J|

